On Heteronuclear Isoelectronic Alternatives to [Au(13)(dppe)(5)Cl(2)](3+): Electronic and Optical Properties of the 18-Electron Os@[Au(12)(dppe)(5)Cl(2)] Cluster from Relativistic Density Functional Theory Computations
Résumé
The development of well-defined atomically precise heteronuclear nanoclusters passivated by protecting ligands is presently a booming area, owing to the fact that doping well-known homonuclear nanostructures allows fine-tuning of their properties. Here, we explore by means of density functional theory calculations the possibility of doping the central gold atom in the classical [Au(13)(dppe)(5)Cl(2)](3+)cluster (1) by Os. Although both [Au(13)(dppe)(5)Cl(2)](3+) and [Os@Au(12)(dppe)(5)Cl(2)] have the same total number of electrons, we show that they are not isoelectronic within the formalism of the superatom model, being respectively an 8- and an 18-electron species. It results that they exhibit similar structures but present significantly different optical behaviors (ultraviolet/visible and circular dichroism). Similar results are obtained for the Ru and Fe relatives. Emission properties indicate some redshift of the T(1)→S(1) decay with respect to [Au(13)(dppe)(5)Cl(2)](3+), involving an equatorial distortion of the Au(12)Cl(2) core in the T(1) state, rather than the axial distortion afforded by 1. The sizable highest occupied molecular orbital-lowest unoccupied molecular orbital gaps found for the three doped species suggest that further experimental exploration of different stable doped species derived from the ligand-protected Au(12)Cl(2) core should be encouraged.
Domaines
Chimie
Fichier principal
Wei_et al_2021_On Heteronuclear Isoelectronic Alternatives_accepted.pdf (1.64 Mo)
Télécharger le fichier
Wei_et al_2021_On Heteronuclear Isoelectronic Alternatives_suppl data.pdf (744.68 Ko)
Télécharger le fichier
Origine | Fichiers produits par l'(les) auteur(s) |
---|